A conjugated two-dimensional polymer film and a preparation method and application thereof

Abstract

The application discloses a conjugated two-dimensional polymer film and a preparation method and application thereof. The preparation method comprises the following steps: placing a copper substrate in a mixed solution containing an organic monomer and a polar solvent, then adding a ligand and performing an interfacial polycondensation reaction, so as to in-situ grow the conjugated two-dimensional polymer film on the surface of the copper substrate. The preparation method provided by the application can in-situ obtain various conjugated two-dimensional polymer films with different bonding connections on the surface of copper. The prepared conjugated two-dimensional polymer film has adjustable pores, a smooth morphology, a controllable thickness and a strong interlayer pi-pi interaction force, and can be widely applied in selective adsorption and separation, photo / electric catalysis, chemical sensing, organic electronics and other fields. Meanwhile, the conjugated two-dimensional polymer film / metal copper composite material prepared in the application can be directly used as an active electrode and applied in electrolytic water, carbon dioxide reduction electrocatalytic reaction and electrochemical seawater uranium extraction.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of organic two-dimensional materials, and relates to a conjugated two-dimensional polymer film and a preparation method and application thereof, in particular to a preparation method of a large-area and continuous organic conjugated two-dimensional polymer film synthesized in situ by using a copper metal catalyzed interfacial polycondensation reaction, and application of the conjugated two-dimensional polymer film. BACKGROUND

[0002] A two-dimensional conjugated polymer is a sheet-shaped structure macromolecule formed by connecting structural units through molecular carbon-carbon double bonds or carbon-carbon triple bonds in the lateral direction, which has the significant characteristics of structural design and functional regulation, and can realize effective regulation of intrinsic properties from the molecular scale or even the atomic scale through means such as design of monomer structure, selection of connecting units and bonding mode. The above characteristics make the two-dimensional conjugated polymer have broad application prospects in many fields, such as selective adsorption and separation, photo / electrocatalysis, chemical sensing, organic electronics, etc. In order to realize the above applications and improve the application performance, synthesis and preparation of a large-area and continuous two-dimensional conjugated polymer become a key problem.

[0003] At present, synthesis of the two-dimensional conjugated polymer is mainly obtained by Ullmann reaction, Schiff base reaction and the like on a metal or highly oriented pyrolytic graphite. However, the two-dimensional conjugated polymer prepared by these methods has problems such as small area (micron level), uncontrollable thickness, difficulty in separation from the substrate, and wrinkles in the film during transfer. In addition, the synthesis of a centimeter-level two-dimensional conjugated polymer has been realized at the gas-liquid interface by the Schiff base reaction, but when the prepared large-area two-dimensional conjugated polymer is transferred to other insulating solid substrates for actual application, wrinkles are also introduced on the polymer film, affecting the performance of the film. Therefore, developing a simple and universal preparation method of large-area and continuous two-dimensional conjugated polymer material has positive significance for the development of many potential fields such as selective adsorption and separation, photo / electrocatalysis, chemical sensing, organic electronics, etc. SUMMARY

[0004] The main purpose of the present application is to provide a conjugated two-dimensional polymer film and a preparation method and application thereof to overcome the deficiencies of the prior art.

[0005] In order to achieve the above-mentioned purposes, the technical solutions adopted by the present application include:

[0006] The present application provides a preparation method of a conjugated two-dimensional polymer film, which comprises:

[0007] The copper substrate is placed in a mixed solution containing an organic monomer and a polar solvent, then a ligand is added and an interfacial polycondensation reaction is carried out, so as to grow a conjugated two-dimensional polymer film in situ on the surface of the copper substrate.

[0008] The application further provides the conjugated two-dimensional polymer film prepared by the preparation method.

[0009] The application further provides the use of the conjugated two-dimensional polymer film in selective adsorption and separation, photoelectrocatalysis, chemical sensing or organic electronics.

[0010] The application further provides a conjugated two-dimensional polymer film / copper composite material, which comprises a copper substrate and a conjugated two-dimensional polymer film grown in situ on the surface of the copper substrate; wherein the conjugated two-dimensional polymer film is prepared by the preparation method.

[0011] The application further provides an active electrode for electrochemical uranium extraction from seawater, which comprises the conjugated two-dimensional polymer film / copper composite material.

[0012] Compared with the prior art, the application has the following beneficial effects:

[0013] (1) The metal copper material adopted in the application is a non-noble metal, which is cheap and easy to obtain, and at the same time, it is both a catalyst for synthesizing a two-dimensional polymer film and a substrate for loading a two-dimensional polymer film material. Due to the good electrical conductivity of the metal copper, the conjugated two-dimensional polymer film / metal copper composite material can be directly used as a working electrode for electrochemical tests, and can be applied to electrocatalytic reactions such as water electrolysis and carbon dioxide reduction, and electrochemical uranium extraction from seawater.

[0014] (2) By changing the type of the metal copper catalyzed polycondensation reaction, the application can realize the preparation of conjugated two-dimensional polymer films with different bonding links (such as carbon-carbon double bonds, thiazole bonds and azo bonds). By controlling the reaction temperature, time and amount of organic ligand, the thickness and morphology of a series of two-dimensional polymer materials can also be controlled.

[0015] (3) The large-area and continuous conjugated two-dimensional polymer film synthesized by the application has adjustable pore channels, smoothness, diversity of skeleton composition, designability of composition and excellent surface post-modification, and has great application prospects in electrocatalytic reactions such as water electrolysis and carbon dioxide reduction, and electrochemical uranium extraction from seawater. BRIEF DESCRIPTION OF DRAWINGS

[0016] In order to more clearly illustrate the technical solutions in the embodiments of the application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or the prior art description. Obviously, the drawings in the following description are only some embodiments described in the application, and for those skilled in the art, other drawings can also be obtained without creative labor.

[0017] Figure 1 A preparation reaction flow chart for in-situ synthesis of conjugated two-dimensional polymer thin film by using metal copper interface-mediated organic polycondensation reaction in a typical embodiment of the present application;

[0018] Figure 2 A display image of the conjugated two-dimensional polymer thin film prepared in Example 1 of the present application on different metal copper substrates;

[0019] Figure 3 An atomic force microscope characterization topography image of the conjugated two-dimensional polymer thin film prepared in Example 2 of the present application in a range of 20 μm x 20 μm;

[0020] Figure 4 A scanning electron microscope image of the conjugated two-dimensional polymer thin film prepared in Example 2 of the present application;

[0021] Figure 5 A UV image of the conjugated two-dimensional polymer thin film prepared in Example 9 of the present application in a seawater uranium extraction process with spiked simulated seawater;

[0022] Figure 6 A principle diagram for in-situ synthesis of conjugated two-dimensional polymer thin film by using metal copper interface-mediated organic polycondensation reaction in a typical embodiment of the present application. DETAILED DESCRIPTION

[0023] In view of the problems in the prior art described above, after long-term research and a large number of experiments, the present inventors have proposed the technical solution, which is mainly based on a solid-liquid interface method, and utilizes the active copper species generated from metal copper in an alkaline and polar solvent to catalyze organic polycondensation reaction for preparing a conjugated two-dimensional polymer thin film at a suitable temperature. Different thicknesses of the thin film can be obtained by regulating the standing time during the preparation process. The conjugated two-dimensional polymer thin film / metal copper composite material prepared by the method can be directly used as an electrode, and the conjugated two-dimensional polymer thin film material can be transferred to any substrate as needed, which is conducive to the construction of application devices with different structures.

[0024] Specifically, as an aspect of the technical solution of the present application, a preparation method of a conjugated two-dimensional polymer thin film includes:

[0025] The copper substrate is placed in a mixed solution containing an organic monomer and a polar solvent, and then a ligand is added and an interface polycondensation reaction is performed, so as to grow a conjugated two-dimensional polymer thin film in-situ on the surface of the copper substrate.

[0026] In some preferred embodiments, the preparation method of the conjugated two-dimensional polymer thin film includes:

[0027] The organic monomers and the polar solvent for the polycondensation reaction are mixed to form a uniform reaction system, the organic monomers can all undergo various organic polycondensation reactions under the catalysis of copper ions, and the organic monomers have a planar structure;

[0028] The clean copper metal is placed in the mixed reaction system and ligands are added, and the copper-catalyzed polycondensation reaction is carried out at a certain temperature, and then a conjugated two-dimensional polymer film is obtained in situ on the copper surface.

[0029] In some preferred embodiments, the preparation reaction flow chart and principle diagram of the in-situ synthesis of the conjugated two-dimensional polymer film by the metal copper interface-mediated organic polycondensation reaction in the present application are shown in Figure 1 and Figure 6 respectively.

[0030] In some preferred embodiments, the organic monomers include any one or a combination of two or more of a cyano monomer, an aldehyde monomer, an amino monomer, and an amino thiol monomer, and are not limited thereto.

[0031] Further, the cyano monomer includes any one or a combination of two or more of p-phenylenediacetonitrile, 1,2,4,5-tetracyanobenzene, 2,2',2",2"'-(ethene-1,1,2,2-tetrakisyltetra([1,1'-biphenyl]-4',4-diy))tetracetonitrile, 2,4,6-trimethyl-3,5-pyridinedicarbonitrile, tetra(4-nitrilephenyl)ethylene, 2,2'-(anthracene-9,10-diyl)diacetonitrile, 2,2"-([2,2"-bipyridine]-5,5"-diyl)diacetonitrile, 2,2'-([1,1':4',1"-terphenyl]-4,4'-diyl)diacetonitrile, 1,3,5-tris(4-cyanomethylphenyl)benzene, 1,3,5-benzene tricyano, 2,6-dicyanonaphthalene, and 4,4'-dicyanostyrene, and is not limited thereto.

[0032] Further, the aldehyde monomer includes any one or a combination of two or more of trimesic aldehyde, 1,3,5-tris(p-formylphenyl)benzene, 1,3,5-tris(4-formylphenyl)benzene, p-phenylenediformaldehyde, biphenyldiformaldehyde, 1,3,5-tris(2-formylpyridin-5-yl)benzene, 2,4,6-tris(4-formylphenyl)pyridine, 1,3,5-tris(4'-aldehyde[1,1'-biphenyl]-4-yl)benzene, 4,4',4"-[benzene-1,3,5-triyltris(ethyne-2,1-diyl)]triformaldehyde, 2,4,6-tris-(4-formyl-biphenyl-4-yl)-1,3,5-triazine, benzo[1,2-B:3,4-B':5,6-B']trithiophene-2,5,8-triformaldehyde, and [1,3,5-trimethyl-2,4,6-tris(4'-aldehydephenyl)]benzene, and is not limited thereto.

[0033] Further, the amino monomer includes any one of or a combination of two or more of tris(4-aminophenyl)amine, p-phenylenediamine, 1,3,5-tris(4-aminophenyl)benzene, 5,10,15,20-tetra(4-aminophenyl)porphyrin, 4-(2-(4-aminophenyl)-12-diphenylvinyl)aniline, 4,4',4"-(1,3,5-benzene triyltris-2,1-ethynediyl)triphenylamine, 4,4',4"-triaminotriphenylmethane, 2,4,6-tris(4-aminophenyl)-1,3,5-triazine, melem, tris(4'-amino-1,1'-biphenyl)amine, 2,4,6-tris(4-aminophenoxy)-1,3,5-triazine, and the like, and is not limited thereto.

[0034] Further, the amino thiol monomer includes any one of or a combination of two or more of 2,5-diamino-1,4-benzenediol dihydrochloride, 3,3'-dithiodianiline, 2- aminobenzenethiol, 3-aminobenzenethiol, 2-aminoethanethiol, 2-amino-4- chlorobenzenethiol, 4-amino-3-fluorobenzenethiol, 3-amino-1,2,4-triazole-5- thiol, 2-amino-5-mercapto-1,3,4-thiadiazole, 2-amino-3-mercaptopyridine, 2-amino-5- methylbenzenethiol, 4-amino-5-phenyl-4H-1,2,4-triazole-3-thiol, and the like, and is not limited thereto.

[0035] Further, the organic monomer includes any one of or a combination of two or more of benzene-1,3,5-tricarboxaldehyde, 1,3,5-tris(p-formylphenyl)benzene, 1,3,5- tris(4-formylphenyl)benzene, p-phenylenediacetonitrile, tris(4-aminophenyl)amine, 1,3,5-tris(4-aminophenyl)benzene, 5,10,15,20-tetra(4-aminophenyl)porphyrin, 2,5- diamino-1,4-benzenediol dihydrochloride, 1,2,4,5-tetracyanobenzene, and the like, and is not limited thereto.

[0036] In some preferred embodiments, the ligand includes any one of or a combination of two or more of piperidine, 2,2'-bipyridine, tetramethylethylenediamine, tris(2- pyridylmethyl)amine, 1,1,4,7,10,10-hexamethyltriethylenetetramine, and the like, and is not limited thereto.

[0037] In some preferred embodiments, the polar solvent includes any one of or a combination of two or more of N,N-dimethylformamide, pyridine, toluene, triethylamine, methanol, acetonitrile, dimethylsulfoxide, and the like, and is not limited thereto.

[0038] In some preferred embodiments, the copper substrate includes any one of or a combination of two or more of copper foil, copper plate, nano-copper, copper wire, copper foam, copper device, copper ornament, and the like, and is not limited thereto.

[0039] Further, the copper substrate is zero-valent copper. In some preferred embodiments, the mass ratio of the organic monomer to the polar solvent is 0.05-5:100.

[0040] In some preferred embodiments, the volume ratio of the ligand to the polar solvent is (0.001-0.05):(1-3).

[0041] In some preferred embodiments, the temperature of the interfacial polycondensation reaction is 60-150°C, and the time is 6-72h.

[0042] In some preferred embodiments, the interfacial polycondensation reaction includes any one of Knoevenagel polycondensation, click polycondensation, and amino self-polycondensation, and is not limited thereto.

[0043] Another aspect of the embodiments of the present application further provides a conjugated two-dimensional polymer film prepared by the aforementioned preparation method, wherein the conjugated two-dimensional polymer film has a porous structure.

[0044] Further, the conjugated two-dimensional polymer film is smooth and flat and has a controllable thickness.

[0045] Further, the thickness of the conjugated two-dimensional polymer film is 50nm-2μm.

[0046] Further, the area of the conjugated two-dimensional polymer film is 1cm 2 -30cm 2 .

[0047] Further, the pore size of the conjugated two-dimensional polymer film is 1nm-3.5nm, and the specific surface area is 50m 2 g -1 -400m 2 g -1 .

[0048] Another aspect of the embodiments of the present application further provides a use of the aforementioned conjugated two-dimensional polymer film in the fields of photoelectrocatalysis, selective adsorption and separation, chemical sensing, or organic electronics.

[0049] Further, the use includes a use of the conjugated two-dimensional polymer film in photocatalytic hydrogen production, carbon dioxide reduction, or electrochemical uranium extraction from seawater.

[0050] Another aspect of the embodiments of the present application further provides a conjugated two-dimensional polymer film / copper composite material, which includes a copper substrate and a conjugated two-dimensional polymer film grown in situ on the surface of the copper substrate; wherein the conjugated two-dimensional polymer film is prepared by the aforementioned preparation method.

[0051] Further, the copper substrate includes a copper foil and / or a foamed copper, and is not limited thereto.

[0052] Further, the copper substrate has a thickness of 0.05-0.5 mm.

[0053] Further, the copper substrate has an area of 1 cm 2 - 30 cm 2 .

[0054] Another aspect of the embodiment of the present application also provides an active electrode for electrochemical uranium extraction from seawater, which includes the aforementioned conjugated two-dimensional polymer film / copper composite material.

[0055] In the present application, the skeleton of the conjugated two-dimensional polymer film is formed by polycondensation of organic monomers, and by using different organic monomers and different polycondensation reactions, conjugated two-dimensional polymer film materials with different pore sizes and functionalities can be prepared, so that the skeleton composition of the conjugated two-dimensional polymer film material has diversity.

[0056] The technical solutions of the present application will be further described in detail below in combination with several preferred embodiments and the accompanying drawings. The present embodiments are implemented on the premise of the technical solutions of the present application, and detailed implementation modes and specific operation processes are given, but the protection scope of the present application is not limited to the following embodiments.

[0057] In the following examples, the experimental materials used in the examples are commercially available from conventional biochemical reagent companies, unless otherwise specified.

[0058] Example 1

[0059] 1. In a quartz tube, 0.0375 mmol of p-phenylenediacetonitrile monomer and 0.025 mmol of trimesaldehyde monomer were dissolved in 1 ml of N, N-dimethylformamide solution.

[0060] 2. Metal copper products such as copper wire, foamed copper, copper devices, copper ornaments, etc. were ultrasonically cleaned with an ethanol solution for 15 min, and then dried by nitrogen blowing. Then the copper foil was completely immersed in the above-mentioned organic solution.

[0061] 3. Then 10 μL of piperidine was added to the organic solution, and the quartz tube was vacuumed and sealed, and then placed in an oven.

[0062] 4. The metal copper catalyzed interfacial Knoevenagel polycondensation reaction was carried out at 60°C for 48 h. After the reaction was completed, the copper metal was taken out and dried, and the conjugated two-dimensional polymer film was grown in situ on the surface of the metal copper. Figure 2 which was smooth and flat.

[0063] Example 2

[0064] 1. In a quartz tube, 0.0375 mmol of p-phenylenediacetonitrile monomer and 0.025 mmol of 1,3,5-tri(p-formylphenyl)benzene monomer were dissolved in 1 ml of N,N-dimethylformamide solution.

[0065] 2. A copper foil with a size of 3 x 1 cm and a thickness of 0.05 mm was cut, ultrasonically cleaned with an ethanol solution for 15 min, and then dried by nitrogen blowing. The copper foil was completely immersed in the above organic solution.

[0066] 3. Then, 10 μL of piperidine was added to the organic solution, and the quartz tube was vacuumed and sealed, and then placed in an oven.

[0067] 4. The copper-catalyzed interfacial Knoevenagel polycondensation reaction was carried out at 90°C for 48 h. After the reaction was completed, the copper foil was taken out and washed and dried, and a smooth and flat conjugated two-dimensional polymer film was grown in situ on the surface of the copper foil. The atomic force microscope image and the scanning electron microscope image of the conjugated two-dimensional polymer film are shown in Figs. 1 and 2, respectively. Figure 3 、 4

[0068] Example 3

[0069] 1. In a quartz tube, 0.0375 mmol of p-phenylenediacetonitrile monomer and 0.025 mmol of 1,3,5-tri(4-formylphenyl)benzene monomer were dissolved in 1 ml of N,N-dimethylformamide solution.

[0070] 2. A copper foil with a size of 3 x 1 cm and a thickness of 0.05 mm was cut, ultrasonically cleaned with a hydrochloric acid-methanol solution for 15 min, and then dried by nitrogen blowing. The copper foil was completely immersed in the above organic solution.

[0071] 3. Then, 10 μL of piperidine was added to the organic solution, and the quartz tube was vacuumed and sealed, and then placed in an oven.

[0072] 4. The copper-catalyzed interfacial Knoevenagel polycondensation reaction was carried out at 90°C for 72 h. After the reaction was completed, the copper foil was taken out and washed and dried, and a smooth and flat conjugated two-dimensional polymer film was grown in situ on the surface of the copper foil.

[0073] Example 4

[0074] 1. In a glass bottle, 0.0375 mmol of p-phenylenediacetonitrile monomer and 0.025 mmol of 1,3,5-tri(p-formylphenyl)benzene monomer were dissolved in 10 ml of N,N-dimethylformamide solution.

[0075] ​2. Cut copper foil with size of 3 x 1 cm and thickness of 0.05 mm, and clean it with hydrochloric acid-methanol solution under ultrasonic for 15 min, and then dry the surface of the copper foil by nitrogen blowing, and then immerse it into the above organic solution.

[0076] 3. Then add 10 μL piperidine into the organic solution, and then vacuumize and seal the quartz tube, and then put it into the oven.

[0077] 4. Perform copper-catalyzed interfacial Knoevenagel polycondensation reaction at 60 °C for 48 h, and then cool it to room temperature, and then take out the copper foil and clean and dry it, and then grow smooth and flat conjugated two-dimensional polymer film on the surface of the copper foil.

[0078] Example 5

[0079] 1. Dissolve 0.0375 mmol of p-phenylenediacetonitrile monomer and 0.025 mmol of 1,3,5-tris(p-formylphenyl)benzene in 10 ml of N,N-dimethylformamide solution in a glass bottle.

[0080] 2. Cut copper foil with size of 3 x 1 cm and thickness of 0.05 mm, and clean it with ethanol solution under ultrasonic for 15 min, and then dry the surface of the copper foil by nitrogen blowing, and then immerse it into the above organic solution.

[0081] 3. Then add 20 μL piperidine into the organic solution, and then vacuumize and seal the quartz tube, and then put it into the oven.

[0082] 4. Perform copper-catalyzed interfacial Knoevenagel polycondensation reaction at 90 °C for 72 h, and then cool it to room temperature, and then take out the copper foil and clean and dry it, and then grow smooth and flat conjugated two-dimensional polymer film on the surface of the copper foil.

[0083] Example 6

[0084] 1. Dissolve 0.025 mmol of 1,2,4,5-tetracyanobenzene monomer and 0.05 mmol of 2,5-diamino-1,4-benzenedithiol dihydrochloride monomer in 10 ml of ethanol-pyridine (v:v = 1:1) solution in a glass bottle.

[0085] 2. Cut copper foil with size of 3 x 1 cm and thickness of 0.05 mm, and clean it with hydrochloric acid-methanol solution under ultrasonic for 15 min, and then dry the surface of the copper foil by nitrogen blowing, and then immerse it into the above organic solution.

[0086] 3. Then add 30 μL piperidine into the organic solution, and then vacuumize and seal the quartz tube, and then put it into the oven.

[0087] 4. Copper foil catalyzed interfacial Knoevenagel polycondensation reaction was carried out at 150 °C for 72 h. After the reaction, the copper foil was taken out and washed and dried. A smooth and flat conjugated two-dimensional polymer film was grown in situ on the surface of the copper foil.

[0088] Example 7

[0089] 1. In a quartz tube, 0.0375 mmol of 1,3,5-tris(4-formylphenyl)benzene monomer was dissolved in 1 ml of N,N-dimethylformamide solution.

[0090] 2. A copper foil with a size of 3 x 1 em and a thickness of 0.05 mm was cut and cleaned with a hydrochloric acid methanol ethanol solution for 15 min. After the copper foil surface was dried by nitrogen blowing, it was completely immersed in the above organic solution.

[0091] 3. Then 30 μL of piperidine was added to the organic solution, and the quartz tube was vacuumed and sealed and then placed in an oven.

[0092] 4. Copper foil catalyzed interfacial Knoevenagel polycondensation reaction was carried out at 150 °C for 72 h. After the reaction, the copper foil was taken out and washed and dried. A smooth and flat conjugated two-dimensional polymer film was grown in situ on the surface of the copper foil.

[0093] Example 8

[0094] 1. In a glass bottle, 0.0375 mmol of 1,3,5-tris(4-aminophenyl)benzene was dissolved in 10 ml of toluene pyridine (v:v = 1:1) solution.

[0095] 2. A copper foil with a size of 3 x 1 em and a thickness of 0.05 mm was cut and cleaned with a hydrochloric acid methanol ethanol solution for 15 min. After the copper foil surface was dried by nitrogen blowing, it was completely immersed in the above organic solution.

[0096] 3. Then 10 μL of piperidine was added to the organic solution, and the quartz tube was vacuumed and sealed and then placed in an oven.

[0097] 4. Copper foil catalyzed interfacial amino self-polycondensation reaction was carried out at 60 °C for 72 h. After the reaction, the copper foil was taken out and washed and dried. A smooth and flat conjugated two-dimensional polymer film was grown in situ on the surface of the copper foil.

[0098] Example 9

[0099] 1. In a quartz tube, 0.0375 mmol of p-phenylenediacetonitrile monomer and 0.025 mmol of 1,3,5-tris(4-formylphenyl)benzene monomer were dissolved in 1 ml of N,N-dimethylformamide solution.

[0100] 2. A copper foil with a size of 3 x 1 cm and a thickness of 0.05 mm was cut, ultrasonically cleaned with a hydrochloric acid methanol ethanol solution for 15 min, and then dried by nitrogen blowing. The copper foil was completely immersed in the above organic solution.

[0101] 3. Then, 30 μL of piperidine was added to the organic solution, and the quartz tube was vacuumed and sealed, and then placed in an oven.

[0102] 4. The copper-catalyzed interfacial Knoevenagel condensation reaction was carried out at 150°C for 72 h. After the reaction was completed, the copper foil was taken out and washed and dried, and a smooth and flat conjugated two-dimensional polymer thin film was grown in situ on the surface of the copper foil.

[0103] 5. The dried thin film can be directly used as an active electrode material for electrochemical uranium extraction from seawater. As shown in FIG. 5, after 20 h of electrochemical testing, the successful extraction of uranium elements in the solution was shown by ultraviolet absorption of the simulated seawater with a standard addition of 100 ppm. Figure 5

[0104] In addition, the inventors of the present application also carried out tests with other raw materials, process operations, and process conditions described in the specification, and all obtained relatively ideal results.

[0105] It should be understood that the technical solutions of the present application are not limited to the above specific implementation cases, and any technical modification made according to the technical solutions of the present application without departing from the purpose of the present application and the scope protected by the claims falls within the protection scope of the present application.​

Claims

1. A method for preparing a conjugated two-dimensional polymer film, characterized by The method comprises: placing a copper substrate in a mixed solution containing an organic monomer and a polar solvent, then adding a ligand and performing an interfacial polycondensation reaction, thereby growing a conjugated two-dimensional polymer film in situ on the surface of the copper substrate; wherein the organic monomer is selected from any one or a combination of two or more of benzene-1,3,5-tricarboxaldehyde, 1,3,5-tris(p-formylphenyl)benzene, 1,3,5-tris(4-formylphenyl)benzene, p-phenylenediacetonitrile, tris(4-aminophenyl)amine, 1,3,5-tris(4-aminophenyl)benzene, 5,10,15,20-tetrakis(4-aminophenyl)porphyrin, 2,5-diamino-1,4-benzenediol disulfide hydrochloride, and 1,2,4,5-tetracyanobenzene; and the ligand is selected from any one or a combination of two or more of piperidine, 2,2'-bipyridine, tetramethylethylenediamine, tris(2-pyridylmethyl)amine, and 1,1,4,7,10,10-hexamethyltriethylenetetramine. The conjugated two-dimensional polymer thin film has an area of 1 cm 2 ~30 cm 2 The conjugated two-dimensional polymer thin film has a thickness of 50 nm~2 μm.

2. The method of claim 1, wherein: The polar solvent is selected from any one or a combination of two or more of N,N-dimethylformamide, pyridine, toluene, triethylamine, methanol, acetonitrile, and dimethyl sulfoxide.

3. The method of claim 1, wherein: The copper substrate is selected from any one of copper foil, copper plate, nano-copper, copper wire, and copper foam.

4. The method of claim 1, wherein: The mass ratio of the organic monomer to the polar solvent is 0.05-5:

100.

5. The method of claim 1, wherein: The volume ratio of the ligand to the polar solvent is (0.001-0.05):(1-3).

6. The method of claim 1, wherein: The temperature of the interfacial polycondensation reaction is 60-150°C, and the time is 6-72 hours.

7. The method of claim 1, wherein: The interfacial polycondensation reaction includes any one of Knoevenagel polycondensation, click polycondensation, and amino self-polycondensation.

8. The conjugated two-dimensional polymer film produced by the production method according to any one of claims 1 to 7, characterized by: The conjugated two-dimensional polymer film has a porous structure. The pore size of the conjugated two-dimensional polymer thin film is 1 nm to 3.5 nm, and the specific surface area is 50 m 2 g -1 -400 m 2 g -1 .

9. Use of the conjugated two-dimensional polymer film of claim 8 in photoelectrocatalysis, selective adsorption and separation, or chemical sensing.

10. Use according to claim 9, characterized in that: The use includes use of the conjugated two-dimensional polymer film in photocatalytic hydrogen production, carbon dioxide reduction, or electrochemical uranium extraction from seawater.

11. A conjugated two-dimensional polymer film / copper composite, characterized in that The copper substrate and the conjugated two-dimensional polymer film grown in situ on the surface of the copper substrate; wherein the conjugated two-dimensional polymer film is prepared by the method of any one of claims 1-7.

12. The conjugated two-dimensional polymeric film / copper composite of claim 11, wherein: The copper substrate is selected from copper foil and / or copper foam, and the thickness of the copper substrate is 0.05-0.5 mm.

13. An active electrode for electrochemical uranium extraction from seawater, characterized in that The conjugated two-dimensional polymer film / copper composite material of claim 11 or 12.

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